CN109577085A - A kind of preparation method and applications of water-resistant type paper surface sizing agent - Google Patents
A kind of preparation method and applications of water-resistant type paper surface sizing agent Download PDFInfo
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- CN109577085A CN109577085A CN201811519814.0A CN201811519814A CN109577085A CN 109577085 A CN109577085 A CN 109577085A CN 201811519814 A CN201811519814 A CN 201811519814A CN 109577085 A CN109577085 A CN 109577085A
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
- D21H21/16—Sizing or water-repelling agents
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Abstract
The invention discloses a kind of preparation methods of water-resistant type paper surface sizing agent, part macromolecule emulsifier, (methyl) styrene, (methyl) esters of acrylic acid mix monomer, deionized water are mixed strong stirring by it, are prepared into lotion；Polymer electrolyte emulsifier, the water of remainder are added to the container, are added initiator after being heated to 80-90 DEG C, after reacting 10-20min, starts that previously prepared lotion is added dropwise to it, time for adding 1.5-3.0hr, cooling discharging after the reaction was continued 1.0-2.0hr；The invention further relates to paper surface sizing agent prepared by the above method and its applications.Present invention styrene-acrylic latex made of emulsifier-free emulsion polymerization, and monomer is added dropwise by the way of first emulsifying monomer, improve the combination of itself and paper surface, the Cypres are coated on paper surface, obtained paper has the characteristics that enhanced water resistance, small-molecular emulsifier is not used in the water-resistant type Cypres polymerization process simultaneously, is environmentally friendly product.
Description
Technical field
The present invention relates to paper surface-sizing agent field more particularly to a kind of systems for the paper surface sizing agent that water resistance is strong
Preparation Method and application.
Background technique
Cypres are the sizing agents for being applied to Paper or cardboard surface, its addition can improve page characteristic or increase paper
Or surface property, intensity and the water-resistance of cardboard.
With the improvement of living standards, requirement of the people to paper quality is also higher and higher, while the development of society is to making
The requirement of paper environment is more and more harsher, because of the research and development a bit to related papermaking chemical product and using more stringent requirements are proposed.Surface
Most of sizing agent mainly consists of two parts: having the hydrophilic group structure of compatibility to the resistive hydrophobic group of water and to paper pulp
At.When glue application solution is applied to paper surface, a part of surface size infiltration fills the gap in page in paper layer；It is another
Part will stay on paper surface.In the drying process, since polymer shows as thermoplasticity, such polymer particle can be in paper
Surface extension is opened to form one layer of continuous film, to improve the performance of paper.
CN104592448A discloses a kind of preparation method of Cypres, and deionized water is added in four-hole boiling flask
And amylase is added after being warming up to 70-90 DEG C in starch, stirring, is continuously heating to 90-100 DEG C, and bicarbonate is added after keeping the temperature 1hr
Then sodium, ferrous sulfate, glacial acetic acid start that monomer is added dropwise, dropping temperature is 85-95 DEG C.It is kept the temperature again after monomer dropping
1hr。
CN107142785A also discloses a kind of cation surface sizing agent and preparation method thereof, utilizes cation denaturation
Acrylyl oxy-ethyl-trimethyl salmiac, acrylamide, benzene second is added as emulsifier in starch, polyvinyl alcohol and span-60
Alkene, butyl acrylate are copolymerized to obtain bronzing cation surface sizing agent.
Two kinds of Cypres are synthesized in the prior art above, the two uses starch or modified starch as dispersion
Agent, and be to be directly added into monomer in monomer dropping mode.Use starch as dispersing agent its glue application solution storage stability not
Height, while it is weak with paper pulp fiber binding force compared to macromolecule emulsifier, water resistance is poor.And it is directly added into the mode of monomer
Often make emulsion particle diameter larger, while distributivity is wider.This makes in the more difficult gap for penetrating into fiber of emulsion particle.
Summary of the invention
In order to overcome the defects of the prior art, the present invention provides a kind of Cypres of water-tolerant and its preparations
Methods and applications use emulsifier-free emulsion polymerization during synthetic surface sizing agent, do not dissociate in such system small
Molecule emulsifier substantially increases its water resistance.Monomer is added dropwise by the way of first emulsifying monomer simultaneously, what is obtained in this way applies
Glue partial size is smaller, and dispersibility is single, and such latex particle can be penetrated into preferably in fibre gap, improve itself and paper
The combination on surface, to can also improve its water resistance.
To achieve the above object, the present invention adopts the following technical scheme:
The first purpose of the invention is to provide a kind of preparation methods of paper surface sizing agent comprising following steps:
Step (1), by part macromolecule emulsifier, (methyl) styrene, (methyl) esters of acrylic acid mix monomer, go from
Sub- water mixes strong stirring, is prepared into lotion；
Polymer electrolyte emulsifier, the water of remainder are added to the container by step (2), are added and are drawn after being heated to 80-90 DEG C
Send out agent；
After step (3), the lotion of step (2) reaction 10-20min, start to lotion obtained in its a dropping step (1),
Time for adding is 1.5-3.0hr, cooling discharging after the reaction was continued 1.0-2.0hr.
In order to advanced optimize above-mentioned preparation method, the technical measures that the present invention takes further include:
Further, the container of the step (2) is any suitable reaction vessel in this field, preferably four-hole boiling flask.
Further, the method for lotion is prepared in step (1) are as follows: 500-800rpm is stirred after macromolecule emulsifier, water is added
Mix, after slowly sequentially add (methyl) styrene, (methyl) acrylate, mixing time 30-40min.
Further, the macromolecule emulsifier of the total dosage 80wt% of Zhan is added in step (1), then in step (2)
Remaining macromolecule emulsifier is added.
Further, the initiator can be added at one time in step (2), and one can also be added in step (2)
Part, remaining part of then slowly dripping in the polymerization reaction of step (3).If initiator is divided into two parts addition,
The initiator of the total dosage 30wt% of Zhan is at least added in step (2), remaining initiation then is added dropwise in step (3) polymerization process
Agent.
Further, in the preparation method, including following component and its parts by weight:
Further, the paper surface sizing agent further includes suitable water, and water is for dispersing each component, this field skill
The needs that art personnel can easily actually use according to product, adjust the dosage of water.It is preferred that 500-890 parts.Certainly, according to production
The needs of product actual use, can also be added suitable quantity of water in inventive formulation to adjust the solid content of final products, such as can be again
The water of 300-1200 parts by weight is added.
Further, the macromolecule emulsifier is selected from polyvinyl alcohol, polyethylene glycol, fatty alcohol polyoxyethylene ether, polyethers
Polyalcohol, polyvinylpyrrolidone, alkyl phenol polyoxyethylene ether, aliphatic acid polyethenoxy rouge, fatty amine polyoxydivinyl ether, polyoxy
At least one of ethylene alkylamine, polydimethyl diallyl ammonium chloride.
Further, described (methyl) acrylic ester monomer is selected from methyl acrylate, ethyl acrylate, the positive fourth of acrylic acid
Ester, isobutyl acrylate, tert-butyl acrylate, Isooctyl acrylate monomer, Tert-butyl Methacrylate, isooctyl methacrylate,
N-propyl, cyclohexyl acrylate, lauryl acrylate, 2-Hydroxy ethyl acrylate, 2-hydroxypropyl acrylate, first
At least one of base methyl acrylate.
Further, the initiator is selected from dibenzoyl peroxide, peroxidized t-butyl perbenzoate, two laurel of peroxidating
Acid, potassium peroxydisulfate, ammonium persulfate, hydrogen peroxide, tert-butyl hydroperoxide, sodium peroxydisulfate, hydrogen peroxide-iron sulfite, sodium peroxydisulfate-
At least one of sodium sulfite, sodium peroxydisulfate-sodium hydrogensulfite, sodium peroxydisulfate-sodium hypophosphite.
Further, the solid content of the Cypres of this method preparation is 25-30wt%, pH 3-4.
A second object of the present invention is to provide a kind of paper for surface sizing of water-resistant type as made from above-mentioned preparation method
Agent.
Third object of the present invention is to provide a kind of application of above-mentioned paper surface sizing agent in paper for surface sizing,
Specifically by the water-resistant type Cypres, according to mass ratio 0.7-1.2:100, (the two is with the oxidized starch after gelatinization
Oven-dry weight) compounding obtain glue application solution, be used for paper for surface sizing.
Compared with prior art, the present invention has the following advantages and beneficial effects:
In the preparation method of water-resistant type Cypres of the present invention, using emulsifier-free emulsion polymerization, while using will
Monomer, which first emulsifies the mode being added dropwise afterwards, can increase substantially the effect of top sizing, and the Cobb value of paper is greatly reduced.This be because
For using emulsifier-free emulsion polymerization, stabilizer of the macromolecule emulsifier as glue application solution greatly reduces and dissociates in emulsion system
Small molecule, to improve the water resistance of paper.It drips after monomer is emulsified simultaneously, it is recognised that closing after partial size is tested
At milk particle partial size it is lower, and dispersibility it is more uniform, this, which allows for latex particle, can preferably penetrate into the gap of paper fibre
In, the binding force of latex and paper fibre is improved, so that the water resistance of paper is also improved.
Specific embodiment
The present invention relates to a kind of preparation methods of the paper surface sizing agent of water-resistant type comprising following steps: by part
Macromolecule emulsifier, (methyl) styrene, (methyl) esters of acrylic acid mix monomer, deionized water are mixed and are stirred strongly
It mixes, is prepared into lotion；The polymer electrolyte emulsifier of remainder, water are added in four-hole boiling flask, are added after being heated to 80-90 DEG C
Initiator after reacting 10-20min, starts that previously prepared lotion is added dropwise to it, time for adding 1.5-3.0hr, the reaction was continued
Cooling discharging after 1.0-2.0hr.The invention further relates to the paper surface sizing agent as made from above-mentioned preparation method and its applications.
With reference to embodiment, the specific embodiment of the present invention is further described.Following embodiment is only used for more
Add and clearly demonstrate technical solution of the present invention, and not intended to limit the protection scope of the present invention.
Embodiment 1
The preparation of water-resistant type Cypres:
By 8 grams of polyvinyl alcohol, 180 grams of mix monomers (100g styrene, 80g ethyl acrylate), 100 grams of deionized waters are mixed
Together in together, 500rpm stirs 30min, forms stable lotion.Four mouthfuls of burnings are added in 350 grams of deionized waters, 2 grams of polyvinyl alcohol
It is warming up to 80 DEG C in bottle, 0.3g ammonium persulfate is added.Aforementioned lotion is slowly added dropwise after reaction 10min, 1.5hr is added dropwise to complete.Drop
0.7g ammonium persulfate, 50g deionized water solution is added dropwise while adding monomer, 2hr is dripped off.The reaction was continued after being added dropwise to complete 1hr.It is cold
But Cypres, pH=3.5, solid content=27.1% are filtered to obtain through 325 mesh filter screens afterwards.
Embodiment 2
The preparation of water-resistant type Cypres:
By 16 grams of octadecyl polyoxyethylene (10) ethers, 200 grams of mix monomers (100g styrene, 100g acrylic acid fourth
Ester), 150 grams of deionized waters are mixed in together, and 600rpm stirs 30min, form stable lotion.By 400 grams of deionized waters, 4
Gram octadecyl polyoxyethylene (10) ether, which is added in four-hole boiling flask, is warming up to 85 DEG C, and 0.3g potassium peroxydisulfate is added.After reacting 10min
Aforementioned lotion is slowly added dropwise, 1.5hr is added dropwise to complete.It is water-soluble that 0.7g potassium peroxydisulfate, 50g deionization is added dropwise while monomer is added dropwise
Liquid, 2hr are dripped off.The reaction was continued after being added dropwise to complete 1hr.Cypres are filtered to obtain through 325 mesh filter screens after cooling, pH=3.35,
Solid content=26.0%.
Embodiment 3
The preparation of water-resistant type Cypres:
By 32 grams of polyvinylpyrrolidones, 180 grams of mix monomers (100g styrene, 80g Isooctyl acrylate monomer), 150 grams
Deionized water is mixed in together, and 600rpm stirs 40min, forms stable lotion.By 310 grams of deionized waters, 8 grams of polyethylene pyrroles
Pyrrolidone, which is added in four-hole boiling flask, is warming up to 90 DEG C, and 0.9g peroxidized t-butyl perbenzoate is added.It is slowly added dropwise after reaction 15min
Aforementioned lotion, 1.5hr are added dropwise to complete.It is water-soluble that 2.1g peroxidized t-butyl perbenzoate, 50g deionization is added dropwise while monomer is added dropwise
Liquid, 2hr are dripped off.The reaction was continued after being added dropwise to complete 1hr.Cypres are filtered to obtain through 325 mesh filter screens after cooling, pH=3.39,
Solid content=29.8%.
Embodiment 4
The preparation of water-resistant type Cypres:
By 8 grams of polydimethyl diallyl ammonium chloride, 180 grams of mix monomers (100g styrene, the tertiary fourth of 80g acrylic acid
Ester), 100 grams of deionized waters are mixed in together, and 500rpm stirs 30min, form stable lotion.By 350 grams of deionized waters, 2
Gram polydimethyl diallyl ammonium chloride, which is added in four-hole boiling flask, is warming up to 80 DEG C, and 1.0g peroxidating tin dilaurate is added.Reaction
Aforementioned lotion is slowly added dropwise after 10min, 1.5hr is added dropwise to complete.Be added dropwise monomer while be added dropwise 3.0g peroxidating tin dilaurate,
50g deionized water solution, 2hr are dripped off.The reaction was continued after being added dropwise to complete 1hr.Top sizing is filtered to obtain through 325 mesh filter screens after cooling
Agent, pH=3.42, solid content=27.3%.
Embodiment 5
The preparation of water-resistant type Cypres:
By 10 grams of polyoxyethylene alkylamines, 200 grams of mix monomers (100g styrene, 100g Isooctyl acrylate monomer), 150 grams
Deionized water is mixed in together, and 550rpm stirs 30min, forms stable lotion.By 400 grams of deionized waters, 2.5 grams of polyoxy second
Alkylene amine, which is added in four-hole boiling flask, is warming up to 85 DEG C, and 0.3g sodium peroxydisulfate is added.Aforementioned cream is slowly added dropwise after reaction 10min
Liquid, 1.5hr are added dropwise to complete.0.7g sodium peroxydisulfate, 50g deionized water solution is added dropwise while monomer is added dropwise, 2hr is dripped off.It is added dropwise
The reaction was continued after the completion 1hr.Cypres, pH=3.39, solid content=26.3% are filtered to obtain through 325 mesh filter screens after cooling.
Embodiment 6
The preparation of water-resistant type Cypres:
By 20 grams of PEG-1000,200 grams of mix monomers (100g styrene, 100g Tert-butyl Methacrylate), 150 grams are gone
Ionized water is mixed in together, and 550rpm stirs 30min, forms stable lotion.400 grams of deionized waters, 5 grams of PEG-1000 are added
Enter to be warming up to 90 DEG C in four-hole boiling flask, 0.3g hydrogen peroxide and 3.0g iron sulfite is added.Aforementioned cream is slowly added dropwise after reaction 10min
Liquid, 1.5hr are added dropwise to complete.10g hydrogen peroxide, 50g deionized water solution is added dropwise while monomer is added dropwise, 2hr is dripped off.It is added dropwise to complete
The reaction was continued afterwards 1hr.Cypres, pH=3.41, solid content=26.9% are filtered to obtain through 325 mesh filter screens after cooling.
Embodiment 7
The preparation of water-resistant type Cypres:
15 grams of polyvinylpyrrolidones are mixed with 150 grams of deionized waters and are stirred with 600rpm, 100g is successively slowly added to
Styrene, 60g 2-Hydroxy ethyl acrylate, persistently stir 40min, form stable lotion.By 510 grams of deionized waters, 10 grams
Polyvinylpyrrolidone, which is added in four-hole boiling flask, is warming up to 85 DEG C, and 1g sodium peroxydisulfate and 1.5g sodium hydrogensulfite is added.Reaction
Aforementioned lotion is slowly added dropwise after 20min, 2.5hr is added dropwise to complete, and 50g deionized water solution is added dropwise while lotion is added dropwise.It is added dropwise
The reaction was continued after the completion 1hr.Cypres, pH=3.37, solid content=28.2% are filtered to obtain through 325 mesh filter screens after cooling.
Embodiment 8
It is glued in tissue paper upper surface:
Comparative example: the sizing agent prepared by the method for Chinese patent CN104592448A embodiment 4 is diluted with deionized water
As a comparison case to 15wt%.
Sizing agent prepared by Examples 1 to 7 formula is diluted to 15wt% with deionized water.
The preparation of glue application solution: preparing 500 grams of 10wt% oxidized starch aqueous solutions, is warming up to 90 DEG C, is gelatinized 20 minutes, cooling
To 40 DEG C, add comparative example and Examples 1 to 7 formula preparation sizing agent (oxidized starch (dry): sizing agent (wet)=50:
3) it, adds water and is diluted to 8wt%.
The measurement of Cobb value:
Using can vigorous absorbability analyzer by GB/T 1540-1989 method detect pattern to be measured.
It is glued in tissue paper upper surface:
Above-mentioned sizing material is used on speciality paper using the glue application solution that comparative example and Examples 1 to 7 formula are prepared, in laboratory
On small-sized sizing applicator, single side sizing is carried out respectively with identical resin added (single side 1.3g/m2), the pattern after sizing is with identical
Temperature, time (150 DEG C of * 20s) are dried on polisher, are measured after pattern curing 5min.Measurement result is shown in Table 1 institute
Show.
1 product performance index of table
| Sample | Cobb value/(g/m2) |
| Blank | 105 |
| Comparative example | 56 |
| Embodiment 1 | 36 |
| Embodiment 2 | 40 |
| Embodiment 3 | 42 |
| Embodiment 4 | 28 |
| Embodiment 5 | 31 |
| Embodiment 6 | 35 |
| Embodiment 7 | 32 |
From it is above-mentioned using result it can be seen that compared with comparative example, can be greatly reduced using Cypres of the invention
The Cobb value of paper, greatly improves its water resistance.
Specific embodiments of the present invention are described in detail above, but it is merely an example, the present invention is simultaneously unlimited
It is formed on particular embodiments described above.To those skilled in the art, any couple of present invention carries out equivalent modifications and
Substitution is also all among scope of the invention.Therefore, without departing from the spirit and scope of the invention made by equal transformation and
Modification, all should be contained within the scope of the invention.
Claims (10)
1. a kind of preparation method of water-resistant type paper surface sizing agent, which comprises the steps of:
Step (1), by part macromolecule emulsifier, (methyl) styrene, (methyl) esters of acrylic acid mix monomer, deionized water
Strong stirring is mixed, lotion is prepared into；
Polymer electrolyte emulsifier, the water of remainder are added to the container by step (2), are added and are caused after being heated to 80-90 DEG C
Agent；
After step (3), the lotion of step (2) reaction 10-20min, start to be added dropwise to lotion obtained in its a dropping step (1)
Time is 1.5-3.0hr, cooling discharging after the reaction was continued 1.0-2.0hr.
2. preparation method according to claim 1, which is characterized in that the method for preparation lotion in step (1) are as follows: be added high
After molecule emulsifier, water 500-800rpm stir, after slowly sequentially add (methyl) styrene, (methyl) acrylate, stir
Time is 30-40min.
3. preparation method according to claim 1, which is characterized in that be added the total dosage 80wt%'s of Zhan in step (1)
Then remaining macromolecule emulsifier is added in macromolecule emulsifier in step (2).
4. preparation method according to claim 1, which is characterized in that reaction system can be added in the initiator in two steps；
Wherein, the initiator of the total dosage 30wt% of Zhan is added in step poly- (2), is then added dropwise in the polymerization process of step (3) remaining
Initiator.
5. preparation method according to claim 1, which is characterized in that in the preparation method, including following component and
Its parts by weight:
6. preparation method according to claim 1, which is characterized in that the macromolecule emulsifier is selected from polyvinyl alcohol, gathers
Ethylene glycol, fatty alcohol polyoxyethylene ether, polyether polyol, polyvinylpyrrolidone, alkyl phenol polyoxyethylene ether, fatty acid polyoxy
At least one of ethylene rouge, fatty amine polyoxydivinyl ether, polyoxyethylene alkylamine, polydimethyl diallyl ammonium chloride.
7. preparation method according to claim 1, which is characterized in that (methyl) acrylic ester monomer is selected from propylene
Sour methyl esters, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, Isooctyl acrylate monomer, methyl-prop
Enoic acid ter-butyl ester, isooctyl methacrylate, n-propyl, cyclohexyl acrylate, lauryl acrylate, acrylic acid -2-
At least one of hydroxy methacrylate, 2-hydroxypropyl acrylate, methyl methacrylate.
8. preparation method according to claim 1, which is characterized in that the initiator is selected from dibenzoyl peroxide, mistake
Aoxidize t-butyl perbenzoate, peroxidating tin dilaurate, potassium peroxydisulfate, ammonium persulfate, hydrogen peroxide, tert-butyl hydroperoxide, over cure
Sour sodium, hydrogen peroxide-iron sulfite, sodium peroxydisulfate-sodium sulfite, sodium peroxydisulfate-sodium hydrogensulfite, sodium peroxydisulfate-ortho phosphorous acid
At least one of sodium.
9. a kind of paper surface sizing agent as made from preparation method according to any one of claims 1 to 8.
10. application of the paper surface sizing agent according to claim 9 in paper for surface sizing, which is characterized in that will
The water-resistant type Cypres compound to obtain glue application solution according to mass ratio 0.7-1.2:100 with the oxidized starch after gelatinization, use
In paper for surface sizing.
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| CN114163569A (en) * | 2021-12-10 | 2022-03-11 | 上海东升新材料有限公司 | Water-resistant surface sizing agent and preparation method and application thereof |
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Application publication date: 20190405 |